CA1296123C - Ionic bond containing polymers - Google Patents

Abstract

ABSTRACT
A polymer has a linear recurring unit in which a first organic group (R1) having at least two carbon atoms and a valence of at least three and a second organic group (R2) having at least two carbon atoms and a valence of at least two are bonded together alternatively through a divalent connecting group, and containing at least one hydrocarbon group (R3) having 10 to 30 carbon atoms which is linked to the reccurring unit by an ionic bond and which may be substi-tuted.

Description

IONIC BOND CONTAINING POLYMERS

Field of the Invention The present invention relates to ionic bon~ containing polymers and more particularly to polymers modified so as to be capable of being formed into a film by the Langmuir-Blodgett method, Description of Prior Art It was found by Langmuir and Blodgett in 1930s that - fatty acids having ca. 16 to 2~' carbon atoms can form a mono-molecular film on the surface of water and such films can be built-up or laminated on a substrate. However, it is o m y in recent years that investigations on their technical applica~
... .
tion has been started. .
Im estigations which have heretofore been made are summarized in Kotai Butsuri (Ph~sics of Solids), 17 ~12), p. 45 (1982); Thin Solid Film, 68, No, i (1980)s ibid,~ 99, Nos, 1, 2 and ~ ~1983); G,L~ Gains, Insoluble Monolayers at Liquid-Gas Interface, Interscience Publishers, New York ~1966)~ and so forth. However, conventional Langmuir-Blodgett films (hereinafter referred to as "LB films") of saturated straight chain carboxylic acids are not satisfactory in heat resitance and mechanical strength and, therefore, cannot be put into practical use as they are.
In order to rectify the above disadvantages, ~ .

12~ 3 1 investigations have been made on poly~eric films of unsaturated fatty acids such as ~ -tricosenic acid, ~ -~eptadecenic acid and ~ -octadecylacrylic acid, fatty acid unsaturated esters such as vinyl stearate and octadecyl acryla~e, or diacetylene derivatives, for example. These filmsl however, are not sufficiently high in heat resistance and cannot be said to be excellent in electrical properties.
It is known that hydrophilic group-containing polymers such as polyacrylic acid, polyvinyl alcohol~ polyethyl acrylate and polypeptid~ also have film-forming properties~ No investi-gation, however, has been made on modified polymers to be used as a material, par~icularly for prepara~ion of ~.B films, and - an excellent LB film material has not yet been discoveredO
Polyimide provides a heat resist~nt film, The thick-~ess of polyimide film produce,l by techniques such as spincoating is greater than 1,000 ~c usually, a heat resistant thin film having a thickness of from 1 ~m to 1~000 A and with no pin hole formed therein is very difficult to produce.
On the other hand, ~ polylmide film is known a~
a heat re isting film but in the cas~ of ~ormLng the ~ilm thereof by spin coatlng, e~c., whic:h is known to bs a coating method for forming the thlnnest ~llm of 6uch a polymerr the thicknes~ of the film form~d i~ at be~t not thlnner than l000 ~ and is usually thicker than about 1 ~mO In other words, it is very dlfficult to form a heat reslsting thin film of thinner than L000 A
havinq no pin holes by u~ing ~uch a polymer.

61~

SUM~LARY OF THE INVENTION
It is an object of the present invention to make it possible to form ~ilms in accordance with Langmuir-Blodget.t technique, by means o~ modification of high polymers which could hardly be formed into a film by Langmuir-Blodgett technique It is another object of the present invention to provide a polymer film which is improYed in heat resistance,.
chemical resistance, and mechanical characteristics such as adhesion force, and which has ~ thickness that could not generally be o~btained.
It has been found that the objects ~an be attained by introducing a substituent t~ impart hydrophobic properties into the recurring unit of pol;ymers.
- 15 The present invention relates to a polymer having a linear recurring unit in which a first organic group, R1l having at least two carbon atoms and a Yalency of.at least 3 and a second organic group, R2, having at least two carbon atoms and a valency of at least 2 are bonded together alter-natively through a divalent bonding group, and containing at least one hydrocarbon group, R3, having 10 to 30 carbon atoms which ;s linked to the recurring unit by ionic ~ond and which may contain a substituent - DETAILED DESCRIPTION OF THE INVENTION
One of LB film materials to be used in the present . invention is a polymer having a linear recurring unit in 129~"3 1 which a first organic group, R1, having at least two carbon atoms and a valency of at least 3 and a second organic group, R2, having at least two carbon atoms and a valency of at least 2 are bonded together alternatively through a divalent bonding roup, and containing at least one hydrocarbon group, R3, having 10 to 30 carbon atoms which is linked to the recurring unit by ion bonding and which may contain a substituent.
Cases in which the valence of R1 is equal to that of 10 R2 or the valence f ~1 is grea.ter than that of R2, but up to 6 are shown below, although the present invention is not limited thereto Valen~e of R1 Valence of R2 1. . 3 2 2. 4 4. 6 6. 4 3 8. 6 3 10, 5 4 11. 6 4 12. 5 13. 6 5 14. ~ 6 6~

1 Al~hough cases wherein ihe valencies of R1 and R2 are 5 or more, compounds in which the valencies of R1 and R2 are up to 4 ~rs preferred.
Specific examples of linear recurring units comprising combinations of Rl a.nd R2 groups having the following.valencies are sho-~rn hereinbelow:
Rl = 3, R2 = 2 Rl = 4, R2 = 2 Rl = 3, R2 = 3 1~ 1 4, R2 = 3 ...
R1 = 4, R2 = 4 ` /
Rl . ~ I~

- - A AB - Rz - B -B

Rl ~ 2) A

Rl ~ 3 O - A BA - R2 - B - _ B
R I ~ 4 j _-- A BA--R2--B ---. . ~ `

/ ( 5 ) ( 6) Rl= valence of 4, :R2= valence of 2 A A
S . R 1 ( 7 ) -- ~ AB--R2--B --A B
. Rl ( 8) -- h AB--R2--B --~ B B
R I ( 9 ) t A AB--R5--B

r ~ A l . - ~Rl ~ ` ~ (lo?

.... -- . ~ A B
R l ( 11 ) --~ A BA--R2--B

. . . ~- B B
. .. -. R l ( 12 ) n A `
5~ 1 ~Rl/ - L (13 t B Bn--R2--A

`` ~.CJ4,'~ 3 A B
R l ~14 ) B B
\ / ~15 ) R1= valence of 3, R2= valence of 3 . A A
Rl R2 ~16) _ ~, A A B B --_ ~ Rl Rz 1 ~17) A AB B

R ~ Rz \ l ~18 A A B B ~

4 ~ 3 . ~ - ., .
i . . ...
,. . : : ", ;.` . . ~ , . :

, .
, ,`., --,.-,,,, . . / / .
;. Rl R2 (19) -- h A B B ----.
, _ .
. ` . -`............................. A P~
.. . ~
- Rl R~ - ~20) . ,.~ . / \ ~ `\
:.. : . ,, -- A BA - B --, . : . ` `:
:'' .--. ' ` ' ''. .
A B
RI R2 . ~21}
.. ` ... ....1 .. / \ / \
.... . . . I -- A B a B --_ .. . .. . ... .
. . .
B A
Rl R2 ~22 -- A B A B ----.. . :- . .
;` . B B
, ,.
. Rl R2 (23) -- A B A B --_ .. ~ .. . .
. . ..: .

: : '. , .,-. . .

.: .
' r~ 3 A A
. .
R I R2 ( 2 4 ) -- B B A A --A B
- Rl R2 ~ ~25) / `~ / ~
-- B B A A --B A
Rl R2 (26) . / `~ / \, -- B B A R --B B
Rl R2 ~27) / `\ / \
-- B B A A --- 5Rl= valence of 4, R2= valence of 3 ~ ~ .
A A ll Rl R2 128) / \ / \
-- A A B B --_ -- lQ ~

`

.,. A A B
\ ./
Rl R2 ~29) ~1 / \ / \
-- A A B B

.. . . ~ A B A-. . R~ R~ ~30) ... ' / '\ / \
: -- A A B B ----. A - B B
.,`. . \ / ~ .
. ~ . Rl R2 (31 . . / ~ / \
-- A ~ B B
..
. . .
.- . . . B B A
., \ /
Rl R2 ~32) / \ / \
-- A A B B

.B B B
\ / /
Rl R2 ~33) / \ / \
-- A A B B
. .

. i~.< 3 . .
.
.. : .. .... ...

.

`
. .
. . A A A
\ /
.. . Rl R2 t34) _-- ll B A B --_ ;' ' - '.
:- A A B
.- . Rl R5 ~35 .. . / \ / '\ .
: -: -- A B a B --. .
: . . :, ,.
. . . A B A
. . - - .... . -. R I R2 t 3 61 . ~ . ./ \ / \
---- A B A B --_ . :- . A B B
. , . \ /
. ..... Rl R2 t37 ''.'. . / \ / \
-- A B A B --.' .-' ' .
. .: . B B A
`' \ / /
- 5 Rl R2 (38) / \ / \
-- A B A B
': ' ;

?~ 3 .
.
` . .

. .

. .
..... .

.,. - B B B
.' " . . \ /
.. ~Rl~ R2 (39) ---- A B A B
: ....
. . .r A A A
-. \ ,/
R l R2 14 0 -- B B A h --_ .. . .

~:. . A R B
,, j . \ ./ /
Rl R2 t41 ~- -- B B A A

A B A
. . . ' . \ ,/
RI R2 t42 . , , -- B B A A ----,. .A B
Rl R2 (43) . / \ / \
-- B B A A --_ .:
' ' ' ' .
I

; .

B B A
\ / /
R1 R2 (44) / \ / \
-- 8 B A ~ --B B B
\ ,/
Rl R2 (45) ,. / `\ / \ '' -- B B A A --Rl=- valence of 4, R = valence of 4 . . .A a A A
\ / \ /
Rl Rz (46) / \ / \
-- A A B B

. A A A B
R I R2 ( 4 7 ) / '\ / \
_-- A AB B ----A B A A
\ / \ /
Rl R2 ~48) / \ / \
-- A A B B ------ . , .
`..' ~ ' .

, . .
, .,. - . A A B B
.' , . . \ ./ \ /
. . l. Rl R2 t49) . / ~ / \
.. - -- A A B B --.
.. A B A B
. ', \ ./ \ /
. - . . R~ R2 ¦ (50) . / '\ / \
. -- A A B B ,J
, Ir . B B A A
.'`-.. '-:.' .......... .. \ ./ \ / .
. - . . Rl R2 (51 ) -. / '~ / \
---- A A B B --~ . .
.. .
.... ; - A B B B
\ ./ \ ~
Rl R2 tS2) A A B B --.:', '' . ~ .
: .
' '7., ' 'B B A B
\ ~ \ /
Rl R2 (53) / \ / \
-- A A B B -- -... .

.

. B B B B
1 - ~ Rl Rz ~ (54) . . A AB B

: . A A A
R I R2 ~ 55 ) ... / `~ / ~
-- A B A B

. . . ~ A A A B 1 . ( 5 6 ) .
_-- A B A B --- . ~- A B A A
.: R 1 R2 ( 57 ?
: , / '\ ~ \
_---- A B A B --- : - ..
a A 8 B
'~, RI R2 ~S8) ---- n B A B

, ~:2~ 3 . ` ` .
`` ..

-- .

..

. - ~ A B A B l .' ., . . \ / \ /
1- Rl R2 ~59 ~. / \ / \
.. -- A B A B --_ . . . ~ ~ B B P, . - .` . Rl R2 - ~fiO) / \ / \
. - ; -- A B A B --; ~ , ! "

~-. . . A B B B .
\ / \ / .. ~
. . - - ~ R l R2 ~ 61 ) ---- A B A B --.. . . B B A B I
.' - . ' \ / \ /
Rl R2 ~62) ` .' / \ / \
_-- A B A B --.
- .: B B B B
^i.:'~:.`--.':. -.`; Rl R2 ~63 / \ / \

.

. .
.
.. ...... -.

; ..

.
- . . A A n A
., , . \ ./ \ ~
1 ~ R l R2 ( 6 4 ) . . . - -- B B A A
.. .. .
~ A A A B
...
Rl R2 - (65) .. , / \ / \
-- BB A A
.. . .
. A B A A ~ .
.. ` .. . .. R 1 R2 . ~ 66 ) . - ~ . . / \ / ~
-- B B A A
:.- - , . .
.
A A B B
: ' \ ~ \ /' ; ........................ Rl R2 ~67 ) .- . / `\ / \
- ---- B B A A --_ '' '' ' -. .
.... . A B A B
.-: b~'~.-.,tX~ R~ R2 (68j .' . / \ / \
-- B B A A
.' :

I B B A A `
Rl R2 1 (69) / \ / \
-- B BA A J

.- A B B B
R 1 R2 t 7 0 ) / \ / ~
_-- B B A A --.. B B A B ~
Rl R2 (71) . / \ / \
-- B B A A --R I R2 ( 7 2 ) / \ / \
-- B B A A

1 In the formulae (1) to (72), AB and BA each represent a divalent connecting group formed by a rection between an acidic group A and a basic group B wherein the groups A and B
contain hetero atoms such as 0, N, S, P and ~ As.examples of such groups, mention may be made of the following~
A~ -COOR (wherein R represents an alkyl group or a hydrogen atom)~ -GOX (wherein X represents Cl or Br and hereinafter referred to as the same meanings), -NCO, -NCS, -CN~ -CONHR, -So2NHR, etc.
B: -NH~, -OR, -SR, -X, etc.
AB~ -CNH-, -CO-, -C:~-, -NHCO- , -NHCS- , -NHCO- , 3 0 ~ ~ O O
-NHCS- , etc.
P o BAI-NHC- , -OC- ,-SC- , -OCNH- , -S2NH~ OCNH-, O O O o O O
-SCNH-, etc.
~ ' In the formulae (1) to (72), there are present A/B
which do not participate in the formation of the linear recurring unitO Through these substituents, at least one, preferably two hydrocarbon groups (R3~ which haYe 10 to 30 carbon atoms, preferably 16 to 22 carbon atoms, and which may have a substituent or substituents are introduced by an ionic bond~ so that film formation can be achieved by Langmuir-Blodgett technique.

1 With regard to A, for example, if A is -COOH, modi-fication thereof is.carried out as follows:

- CON ~ R4 Rs O H

R4 and R$ are each a hydrocar~on group having 1 to 30 carbon atoms which m~y be subs~itu~ed~ or a hydrogen atom, and pre-ferably a hydrocarbon group ha.ving 1 to 4 carbon atoms or a hydrogen atom, With regard to B, if E. is -NH2, -NHR4, or -N~R4 , ~odification thereof is carried out as follows:

- NH30CR3 - ~H20CR:~ - NHOCR~
Il l 11 /\ 11 C , R4 0 , R4RsO

wherein R4 and R5 are as defined above.
Rl and R2 in the general formulae (1) to ~72) are each at least trivalent group and at least divalent group, respective-ly, having at least two carbon atoms, preferably 5 to 20 ~rbon atoms.

~" ~ j? ~ ~
i It may be an aromatic group; an alicyclic group; an-aliphatic group; a ~roup wherein an aromatic group and an aliphatic group are combined, a ~roup wherein each of the above-mentioned groups is substituted by a monovalcnt ~roup having 1 to 30 carbon atoms selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group, and a group in which an aliphatic group is combined with an alicvclic group or an aromatic group; or a group wherein each of the preceding gr~ups is substituted by a monovalent group such as a halogen atom, nitro group, amino ~roup, cyano group, methoxyl group or acetoxyl group~ or by a group in which the above ~.onovalent group bonds to -0-, -C00-, -NHC0-, -C0-, -S-, -CSS-, -NHCS-, -CS-, or the like.
Groups characterized by benzenoid unsaturation having at least 6 carbon atoms are preferred as Rl in points of heat resistance, chemical resistance and mechanical properties.

The term "benzenoid structure" refers herein to the structure of carbocyclic compounds as contained in ordinary aromatic compounds, as contrasted with quinoid structures.

p-qu inoid lZ5~23 As specific examples of F~1 and R2 mention may be made of the followings t ~} ~=;~R

5 whe re in R6 repre se nt s Cll3 CF3 -- (CH2) n --..: (n = 1 ~ 3) ~--C --, -C --.

-- O --, -- C O --, -- S -- , --SOz --, --N--. --Si--, --O --Si--O--.

- O - ~ - O -, - I -Il 11 O O

( in whic~i R7 represents an alkyl group or an ~ryl group ) .

~H3 ; ~---C H 2--C ~ o _~3 C - C H 2 :~2~f~123 Cl13 C~13 - (CH2)4C ~ C - (CH2 )4 -- Cl13 CH3 - CHz CH2 , CH2 CH:~
- (CH2)p-(p = 2 ~ 10) .- (CHz)4 - C --(CH2) 2 , , ~ 11 - (CH2)3-C - (CH2)3 - ,-- (CH2)- C - (CH2)3 - , - (CH2hoCH - CH3 , - (CH2)3 - C-(CH2)2 - , - (CH2)3-0 - (CH2)2-0 (CH2)3 - , CH3 . CH3 CH3 CH3 - CH2 - C(CH2)2C- CH2 - , - CH2C (CH2)2C -(CH2)2 .
H H

-~ .

123~1 ~3 . .

.
. .

-' , ':
.
. . CH3 CH3 ., . . I . I
(CH2~3-Si-O-Si- (CH2)3--.. . - ' I I
CH3 Cl13 .. ... CH3 CH3 - I I .
- -- (CH2)4-Si^O-Si- (CH2)3--..... :. ,................................ I I
... - CH3 CH3 . . ' . i '. r .

-- . -- (CH2)3 - Si--O --Si- (CH2)3 --. I I
. -. C6 H6 C6 H6 .
. ' . :... .
. .
.. , . . CH3 C1i3 C113 CH3 - ' ' ~ li-O-SIi~ ' - CH3 Cl13 . :

6~ 3 : ' . . . - , . .
`

.
. ... . . .
....
`` '': ' :-.''' ' .' .
C H ~ C H 3 1. -- (CH2)3 - Si--O --Si- (CH2)3--C~ Hs C6 Hs ...
, . . CH3 CH3 CH~
; - . I I
-- (CH2)3 Si--O --Si--O- Si- ~CH2)3--I I
CH3 CH3 CH~
.. .. . . .
.. .
' - - CH3 Cl13 - CH3 .. I
-- (CH2~3 Si--O- (Si-O~n-Si- (CH2~3 --- l l l [n = 2 ~ 1 5 ., ,.i,,-., ..-. j.

.

, 1'~ 3 ~ .~

R

(R6 is the same as defined abo~e).

S ~ ~ R~- ~

(R6 is the same as defined above~O

- 2~ -~, 5 ~ ~ 3 As more preferred exampl.es of R1 and R2 . mention may be made OI the followings ~3 ~-R~

S ~ `~~, ~.

~ ~ {3 ~

~R6 ~ ~

~,~

,~ ~R

(R6 is as defined above).

~ .'23 1 The above examples are desirable in that they easily form a ~-membered ring and a 6-membered ring in the cycli~a-tion reaction.
R3 is a hydrocarbon containing group having 10 to 30 s carbon atoms, preferably 16 to 22 carbon atoms. h preferred example thereof is a monovalent group selected from an aliphatic group, a connecting group of alicyclic group and aliphatic group, a connecting group of aromatic group and aliphatic group, or substituen~s thereof. As specific examples of R3, mention~may be made of t;he followings~

(CH3) (C~l2)n-l , CH2 = CH (CH2)n-2 . ~CH (CH2) n-3 , CH~(CH2)~C 9 C-C 9 C(CHz) m CH3~ C(CH2)n-4 , ~ (CH2)n-6 -(CH2)n-s - ~ tCH2) n-6 -~ 3 1 (in which Q + m=n - 5, and n is an integer of from 10 to 30, preferably from 16 to 22).
Particularly preferred examples are straight chain aliphatic hydrocarbon groups These groups may be substituted with substitutional groups t such as a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group and the like, although they are not critical. Fluor ~ atom can be pre-ferable as a substitutent in some cases s;nce it is capable - 10 of imparting .-~igher hydrophobicity to the polymer than . hydrogen.
In other words, alkyl groups having a shorter chain can be employed when fluorine atoms are contained therein~
For example, in the case of.C8F17(CH2)k-,(k=2)will be suffi-15 cient to obtain a high polymer capable of forming a film - Specific examples of high polymers employable in the film forming process of the present invention will become apparent by apply;ng the examples of R1~ R2, R3, A, B, AB
and BA, as well as the modes of substitution of R3, to the formulae ~1) to (72), Although the formulae (1) to (72) do not include copolymers, it is a matter of course that copolymeric deivatives and mixtures thereof are included within the scope of the present invention.
Furthermore, although it is not indispensable, the high polymer of the present invention may be substituted by 36~ ~3 1 groups having 1 to 9 carbon atoms.
There are no particular limitations to the molecular weight of the high polymer of the present invention. A film can bè formed in accordance with the film-forming,process of the present invention even when its molecular weight is low.
In such a,case,, however, it may not be possible to attain good heat resistance, mechanical strength and chemical resistance, On the other hand, an excessively high molecular weight is undesirable since it may become difficult ts form a film because~of an increase in viscosity~
Accordingly the number average molecular weight is preferably frcm ~x~t 2,000 to ~x~t 300,000, preferably 10,000 to 15,000.
Specific examples of the high polymers of the present invention which are derived from the formulae (1) to (72) are shown below.

~ ' ~ ..
1~ ~R 3 C~ 114 3 N h O O

. .

r ~ R 3 ¦

~NIl N ~4 ~N
O O

' ''` "' ''`''' ' " .
. :. .' ' ,,, ,.:, .

, .:.
. ,'' . O O
R 3 ¢~ R 3 R4~NOC CON~R4 .. H ~ 1~ I R 5 ( ~ ~) : ' _--NH~R~ NHICî ~li _ - O O
"; ' '' ''' ; ~ e Rl~ R~ 1 : .. . t N ll 3~ ( 7 6 ) ., . . .O O
',-~' CON~R4 NHR3 .- . . 1~ H 1~ ( 7 7 ) 3~ --C~C N H /~\ N H--_ -O O ~ .

'' ' ' ' '- . -. , .

..
.
.. ..
. . . o o R3 ~ R3 . . R~ ~ NOC CON ~ R4 . . , . R5~ 1 ~ I ~ NH2 ~7B) _ C CNH NH - _ .,, ,,~ ~ O O
.
.
"' .:. .. .' ~ O O O `
. ; . R3 ~Q~ R3 . .-- . . R4 ~ NOC CON ~ R~ H2NC NH - _ .
. . -.... .: .. I ~ ~ H ~ (793 . . . ICl CNH
. -, .............. ' . ~ O O
.
.. . . .

O O
. R3 ~9~ R3 R4 ~ NOC CON ~R4 NH2 NN2 . R5 1 ~ I ~ (80) C CNH NH _ ~ 11 .

. . - 3~ -1~9b~L~3 .
. . -.
. .
-.". -................... ' o o o R3~11 II~XE) R 3 ll R43~NOC CON~R4 Nl12C NH
1~ R51 )~ I 'R5 )~( ~81) .. _ C C NH CNH2- _ . : 11 11 11 .'':'' ~ ~ O O O
.-. ~
... ... ; .:. R3 ~8 8~ R 3 L.. : . . R4~NOC CON ~R4 . ;' .. -', X`~

. C C--N~_ N _-- ~82) . . . ~ O O R4 R4 .
. ' -; -,`... : ' ~ O `
~) R3 , ",,~ y ~ ~CON~

. . O o ... .

9~L"3 : ' , . ... - .. , . .. .
.,. .- ~ O O ~
. R3 6~ I~E) Rl .
- R4~NOC ,~,;,CON ~R2 - ~C~50~0r~8o O O
- .-. .
.. ` -- ` R4 R4 . .. 11 1 ~

- . ` . : --C O~ C O ~ ~ 8 5 ) ...
.~,.; .
.-` . ; ~ O Q
R3 ~11 11~10 ,R3 R4~NOC CON~R4 _ Rs' I )~( i `1' ` (86 ".,.j.- O ~__ ':` '' - ' .
.

1~ In the above formulas, " -~" indicates isomerism. For instance, formula (~,~3) stands for formulae . .
(73-1) and (73-2) shown below.

. ~ O
~ R 3 ~ C ~ NH ~ ~ Nl: ¦

~ . . . .
.. o ~

S ~ H I N ~ , -NH +

~ .
. ~ CNH ~ NH

-C CON ~R4 ~73-2 11 11 I Rs ~O O H

~3 1 The present invention includes not only the case where either (73-1) or (73-2) exist but also the case vlhere both of them coexist, Other examples will be found in books, for example, Heat Resistance of Polymers.(March 5, 1970) and Thermal De-com~osition and Heat Resistance of Polymers (March 15, 1974), both edited by Hirotaro Kambe and published by Baifukan Co., Ltd.
A process for production of the above ion bond-contain-ing polymers wlll hereinafter be explained with reference tothe ~ w~ n the formula (73), ~erein ~=CH3(CH2)17 , 4 ~ 3 Trimellitic acid is acylated with thionyl chloride in an organic polar solvent under substantially anhydro~s conditions and,then reacted with p-phenylenediamine at a temperature of about O to 400C, preferably about 20C to form polyamide acid having a recurring unit represented by the . ' formula~
~ O ~

C ~ C N ~ N
O O ll H

1 The molecular weight of the formed polyamic acid greatly varies with the reaction conditions empolyed, such as reaction temperature, purity, degree of purification, and water content of reagents and sol~ents, ratio of acid component 5 to diamine component, order of addition and the like.
In order to obtain high molecular weight polymers, it is desirable that the reaction be carried out at low tempera-tures, using a reagents and solvent of high purit.y and low water content, and the ratio of the acid component to the 10 diamine component be approached to 1 as close as possible. In a preferred embodiment of the present invention~ the polyamide acid salt is not always of high viscosity and, therefore, it - can be very easily prepared with no severe control in condi-i .
tions. ..
To the polyamide acid thus obtained is added a solu-tion of N-n-octadecyldimethylam.ine. It ls also possible that a solution of N-n-octadecyldimethylamine in-a mixed solvent of dimethylacetamide and benzene is mixed with a diluted solution of polyamide acid in a solvent (e.g., a mixture of dimethyl-20 acetamide and benzene tlll)) to form a solution of the salt of the present invention, and that the solution of the salt of the present invention be used as it is, as a spreading solution for the production of LB films.
A process for production of LB films to be used in 25 the present invention will hereinafter be explained.

. - 39 -1In a process for formin~ a Langmuir-Blodgett film, a film-forming material is spread on the surface of water, and the thus spread material is compressed at a certain surface pressure to form a-monomolecular film, which is then trans-ferred or laminated onto a substrate by passing the substrate through the film. This is known as the vertical dipping method.
Other known processes for forming a Langmuir-Blodgett film include the horizontal dipping method, the revolving cylin-drical method, etc. (see Shin Jikken Ka~aku Koza1 Vol, 18 1-0(Surface and CoIloids), pp. 498-508. Any conventional proce-sses can be applied to the present invention without any particularly restrictions.
The Langmuir-Blodgett pr~cess is an excellent method for forming oriented thin films of less than 1,000 A, or of several hundreds A or several tensA, The thickness of the thin films can be controlled with an accuracy of some tens A
and the films formed on a substrate in accordance with the present invention also have the same characteristics, In accordance with this methodt it is possible to form a film having a thickness greater than 10,000 A.
.
It is known that if the aboye polymers are mixed with known Langmuir-Blodgett film compounds, the film forming pro~
perty is improved. This is a preferred embodiment of the present invention.

12~36~23 1 Known Langmuir-Blodgett film compounds are des-cribed in the ab~ve-cited references and are well known in the art, In particular, compounds having a hydrocarbon group having about 16 to 22 carbon atoms ænd a hydrophilic group, as represented by the following formulae are preferred.

CH3(CH2)n-1Z
CH2=CH(cH2)n-2z CH3(CH2)Q C-C~c-c(CH2)mZ
(wherein n=16 to 22. Q +m=n-~, and Z=OH, NH2, NHR', NR'R', COOH, CONH2, oooRl/ etc. (wherein ~' is a lower aliphatic hydro-carbon group)), In improvement of film forming properties, compounds represented by the formula~ CH~j(CH2~n_1Z are excellent from a viewpoint of cost, Compounds having an unsaturated bond have a feature in that they are polymeriable upon irradiation of e.g,, light or radiations.
The mixing ratio of at least compound selected from the above compounds $o the polymer is not critical in the present invention.
In spreading the component forming a film on the surface of water according to the Langmuir-Blodgett process, solvents insoluble in water and vaporizable into the gas phase, such as benzene chlorofor~.and the like, are used. In the case of the polymers of the present invention, it is desired to use organic polar solvents in combination in order to improve ~ r~ '3 1 the solubility. Preferred organic polar solvents are N,N-dimethylformamide, ~,N-dimethylacetamide, N,N-diethylform-amide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethyl-sulfone t hexamethylphosphoramide~ tetramethylensulfone, di-methyltetramethylensulfone and the like.
Accordingly, in a case where the polymer of the pre-sent invention and known Langmuir-Blodgett film compound are spread, a mixed solvent of a solvent such as benzene and 10 chlofor~ and ah organic polar solvent is preferably used.
In the case where an organic polar solv~nt is used in combination.with a volatile solvent such as benzene, F chloroform, etc., it is presumed that. the latter vaporizes into the gaseous phase during the spreading, whereas the ~ormer 15 dissolves into the large quantity of water.
There is no particular limitation to a ~,ind of a æubstrate to be used in the present invention. It depends only on the use or application of the film. Examples of sub-strates which can be used ;n the present invention include those made of ordinary inorganic substànces, such as glass, alu~a quartz, etc.; those made of metals, plastics and semi-conductors of e.g., Groups IV, III-V and II-VI of the Periodic Table such as Si, GaAs and ZnS and those made of magnetic materials or ferroe ~*ric materials, such as PbTiO~, Ba~iO3, 25 L~03, IiTaD3, etc. It ls also possible to use a substrate _ 42 ~

1 subjected to a conventional surface treatment.
The adhesion between the high polymer film of the present invention and a substrate can also be improved by applying a silane coupling agent (in particular, a silane coupling agent such as A-llO0, A-187, etc., produced by ucc,containin~ an amino group and an epoxy group) or an aluminum chelate to a substrate followed by sub~ecting it to a heat treatment.
It is a feature of the present invention that a thin film of 2 polymer having a good heat resistance can be formed on a substrate in accordanc~ with the Langmuir-Blodgett process. It is another feature of the present invention that some of the films can be subjected to a partial or complete ring-closing treatment, in order to further improve the heat resistance of the thin film formed on the substrate.
Of the examples represented by the formulae (73) to (86~, the ~ormulae (73) to ~82) indicate examples capable of being ring closed, partially or completely, into the 5- or 6-membered ring having a hetero atom. Structures after the ring is completely closed are shown below.

. 12961'3 ¦ ¦ N- ~ ~N4 ~ (73/

~NN 1:~3C ~-- (74) ':.` O

- ~R~l (75) ... .

1~96~L~.'3 . . .

.
. R4 R4 C~ )~ \C ~ 7C) .. :: , .- .
` . : , ( 77 ) ''.'.-. . i O

~N
. 11 .. .. , ................... ~

.
..;,.-.
.'':`'"- ' - .

s `

3~ 23 `-.

. . . ` : .
.. . . .. ~ ., -. - ,.

(79) - O

5 ~ ~
O O
, ~ ~ ~

~ ~ ~ C )~ C
",., ,. ,., , ~ ~

.. . . N~ ~ ~

.s~ _ C ~N ~C ~ 81 i . . . _ C~ O
,,:.,'` ' ~, , ~

~o ~ ~
ll ll ~ ` ~3 --( 8 2 ) ~ B o .

~ ~ 6 1 ~3 l There is no special limitation to the method of the ring closure. It is preferred to use chemical curing agents to be used in curing of polyamic acid, such as acetic anhydride and pyridine 0~ course, heat or light may be used s in combination.
In order to obtain a thin film having good heat resis-tance by the ring closurel a kr,own Langmuir-Blodgett film compound to be mixed is preferably selected from the above listed compound which are soluble in solvents under the ring closure conditions~
The usè of the thin film will hereinafter be explained.
The thin film of the present invention can be used in a variety of fields, including such fields as electronics, t energy conversion and separation of subst~nces,-by making use - 15 of its characteristics that it has good heat resistance, chemical resistance and physical properties and i~ ln the form of an extremetly thin film.
In the field of electronics, the film of -the present invention can be used as an optical recording film, a resist 20 film, an insulating f;l~b a ffiin film for c:a~acitor, an orientation film for liquid crystal, a polarization film, a sensor film, etc., making use of its electrical conductivity, photoconductivity, optical characteristics, electrical insulating properties, thermal characteristics and chemical reactivity. In particular, as an insulating film, the film can be used as an insulating ~g6~J_3 1 layer in electrical or electronical devices having the structure, such as MIS and MIM, in which as an insulating layer of IC and LSI, various se~iconductors and metals are used in combination, and can constitute a Field Effect Transister photoelectric converter, light-emitting device, light-receiving device, light-detecting device, hot electron transister, and the like. In particular, the thin film of the present invention is effective in MIS

and MIM devices utilizing the tunnel effect and can be 10- used as an insulating film of Josephson Janction (JJ) device.

In addition, the thin film of the present invention can be expected to be used as a cladding material for wave-guide or an optical circuit component.

The thin film of the present invention is thought to be suitable as a protective coating material. Various functions can be realized acccrding to the technique for forming mixed and layered films by using the high polymer of this invention in place of conventional L~ materials-.

Such a mixed or layered film has a variety of uses. For example, a photoelectric converter or a biosensor can be prepared from a film incorporated with a dye or an enzymeO
In addition, the thin film : can be expected to be used in separation of substances.

The present invention is described in greater detail with reference to the following examples.

~96~ ~3 1 EXAMPL~ 1 1.92 g (0.01 mol) of trimellitic anhydride was dessolved in 40 cc of dry hexamethylphosphoramide and then cooled to 0 to 5C under a stream of dry nitrogen. Then 1.19 g of thionyl chloride was dropped, and'the resulting mixture was maintained for 1 hour to complete acylation of the trimellitic anhydride. Then a solution of 1.08 g (0.01 mol) of p-phenylenediamine in dimethylacetamide was - dropped at about 20C, and after the completion of addi-tion, they were reacted for 2 hours.
The reaction mixture was di'luted with a mixed solvent of dimethylacetamide ~nd benzene (1:1) to form a t solution of 1 x 10 3 M and the solution was mixed and reacted with a 2 x 10 3 M solution of N-n-octadecyl dimethyl-amine in a mixed solvent of dimethylacetamide and benzene (1:) to prepare a spreading solution for LB films.
In the measurement of the ionic bond containing polymer of this example on reclistilled water at 20C, it - was found that when the area per the recurring unit reached O~
23 about 130A~, the 'surface pressure rose, thereby forming a condensed film. The critical area was about 120A2. When the film on the surface of water was built-up on an aluminum evaporated glass substrate by the LB method, there was obtained a built-up film of the Z-type. In the FT-IR-ATR
analysis of the built'-up film, there were observed an absorption characteristics of the alkyl group at from 3,000 ~ ~36123 1 to 2,800 cm ~ and of the salt at from 1,650 to 1,600 cm 1, respectively.
Wheh the laminated film was subjected to chemical curing with pyridine and anhydrous acetic acid, the absorp-tions due to the alkyl group and the salt disappeared andan absorption due to the imido bond appeared. This clearly shows that the imiization reaction occurred.

2.18 g (0; oi mol) of pyrromellitic acid dianhydride was added to 50 cc of dry dimethylacetamide in a flask, and 1.51 g (0.01 mol) of 2,5-diaminobenzamide dissolved in 30 cc of dimethylacetamide was dropped at about 20C under a stream of dry nitrogen o~er about 10 mihutes, and the reaction was allowed to continue for 2 hours, after completion of the dropping. The reaction mixture was diluted with a mixed solvent of dimethylacetamiae and benzene ~1:1) to form a solution of 1 x 10 3 M and the solution was mixed and reacted with a 2 x 10 3 M solution of ]~-n-octadecyl dimethyl amine in a mixed solvent of dimethylacetamide and benzene (1:1) to - 20 prepare a spreading solution for LB films.
The surface pressure-area cur~e of the ionic bond containing poly~er of this example was obtained by measurin~
at 20C on the surface of redistilled water. When the area per the recurring unit approached to about 150 A , the surface pressure rose, thereby forming a condensed film.

1 The critical surface area was about 140 A2. When the film on the surface of water was built-up on an aluminum evapo-rated glass substrate by the LB method to obtain a built-up film of the Z-type~

2~72 g (0.01 mol) of benzidine-3,3'-dicarboxvlic acid was dissol~ed in 50 cc of dry hexamethylphosphoramide under a stream of dry nitrogen in a flask, and 2.03 g (0~01 mol) o terephthalic acid dichloride dissolved in 30 cc of dry di-lQ methylacetamide was dropped at about 20~C and the reaction was allowed to continue for about 2 hours after completion of dropping. The reaction mixtur~ was diluted with a mixed solvent of dimethylacetamide a~d benzene (1:1) to form a solution of 1 x 10 3 M and the solution was mixed and reacted with a 2 x 10 3 M solution of ~-n-octadecyl dimethylamine in a mixed solvent of dimethylacetamide and benzene (1 1) to prepare a spreading solu~ion for LB films.
The surface pressure-area curve of the ionic bond containing polymer of this example was measured on the surface of redistilled water at 20Ce When the area per the recurring unit approached to about 140A2, the surface pressure sharply rose, thereby forming a condensed film.
The critical surface area was about 130 A . The film on the surface of water was built-up on an aluminum evaporated glass substrate by the LB method to obtain a built-up film of the Z-type.

'3 1 A thin film can be formed by the LB method using the ionic bond containing polymer of the present invention. When the LB film thus obtained is subjected to the ring closure reaction, there can be obtained a ultra thin film which is good in heat resistance and electrical characteristics, and in chemical resistance and mechanical characteristics, and which has a thickness of not more than 10,000 A, and if desired, 10 to 1,000 A.
While the invention has been described in detail and with reference~to specific embodiment thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
t~ .
..

Claims (11)

1. An ionic bond containing polymer having a linear recurring unit in which a first organic group (R1) having at least two carbon atoms and a valence of at least three and a second organic group (R2) having at least two carbon atoms and a valence of at least two are bonded together alternatively through a divalent connecting group, and containing at least one hydrocarbon group (R3) having 10 to 30 carbon atoms which is linked to the recurring unit by an ionic bond and which may be substituted by a member selected from the group consisting of a halogen atom, a nitro group, an amino group, a cyano group, a methoxyl group or an acetoxyl group.

2. The polymer of Claim 1 wherein the recurring unit contains two hydrocarbon groups (R3).

3. The polymer of Claim 1 wherein any one or both of the orgainc groups R1 and R2 is a benzenoid group having at least 6 carbon atoms.

4. The polymer of Claim 1 wherein the hydrocarbon group R3 is an aliphatic group, a group resulting from bonding an alicyclic group and an aliphatic group, a group resulting from bonding an aromatic group and an aliphatic group, or each of the above groups which is substituted by a member selected from the group consisting of a halogen atom, a nitro group, an amino group, a cyano group, a methoxyl group or an acetoxyl group.

5. The polymer of Claim 1 wherein the recurring unit is a precursor for forming a 5- or 6-membered ring containing a hetero atom.

6. The polymer of Claim 5, the 5- or 6-membered ring containing a hetero atom, is formed by curing a built-up film.

7. The polymer of Claim 1 wherein the number of carbon atoms of the hydrocarbon group R3 is from 16 to 22.

8. The polymer of Claim 2 wherein any one or both of orgainc groups R1 and R2 is a benzenoid group having at least 6 carbon atoms.

9. The polymer of Claim 2 wherein the hydrocarbon group R3 is an aliphatic group, a group resulting from bonding an alicyclic group and an aliphatic group, a group resulting from an aromatic group and an aliphatic group, or each of the above groups which is substituted by a member selected from the group consisting of a halogen atom, a nitro group, an amino group, a cyano group, a methoxyl group or an acetoxyl group.

10. The polymer of Claim 2 wherein the recurring unit is a precursor for forming 5- or 6-membered ring containing a hetero atom.

11. The polymer of Claim 2 wherein the number of carbon atoms of the hydrocarbon group R3 is from 16 to 22.